Tuning the Topology of Two-Dimensional Covalent Organic Frameworks through Site-Selective Synthetic Strategy.

Tuning the topology of two-dimensional (2D) covalent organic frameworks (COFs) is of paramount scientific interest but remains largely unexplored. Herein, we present a site-selective synthetic strategy that enables the tuning of 2D COF topology by simply adjusting the molar ratio of an amine-functionalized dihydrazide monomer (NH2 -Ah) and 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tribenzaldehyde (Tz). This approach resulted in the formation of two distinct COFs: a clover-like 2D COF with free amine groups (NH2 -Ah-Tz) and a honeycomb-like COF without amine groups (Ah-Tz). Both COFs exhibited good crystallinity and moderate porosity. Remarkably, the clover-shaped NH2 -Ah-Tz COF, with abundant free amine groups, displayed significantly enhanced adsorption capacities toward crystal violet (CV, 261 mg/g) and congo red (CR, 1560 mg/g) compared to the non-functionalized honeycomb-like Ah-Tz COF (123 mg/g for CV and 1340 mg/g for CR), underscoring the pivotal role of free amine functional groups in enhancing adsorption capacities for organic dyes. This work highlights that the site-selective synthetic strategy paves a new avenue for manipulating 2D COF topology by adjusting the monomer feeding ratio, thereby modulating their adsorption performances toward organic dyes.

Structural Comparisons, Fluorescence Properties, and Glass-to-Crystal Transformations of Heat-Cooled and Melt-Quenched Zeolitic Imidazolate Framework Glass.

As a representative of zeolitic imidazolate framework glass, agZIF-62 has been reported to be synthesized using a melt-quenching method in which the ZIF-62 crystal is heated to a temperature above the melting point. Interestingly, we unexpectedly found that agZIF-62 can also be synthesized by simple heating at temperatures lower than the melting point, which may be assisted by the release of encapsulated solvent molecules. The structural differences between melt-quenched agZIF-62 (MQ-agZIF-62) and heat-cooled agZIF-62 (HC-agZIF-62) were investigated. The results indicated that MQ-agZIF-62 is closer to the liquid state, while HC-agZIF-62 is closer to the crystal state. Interestingly, their luminescent emissions exhibit significant differences. Compared with the ZIF-62 crystal, MQ-agZIF-62 showed a blue-shift of 14 nm, whereas HC-agZIF-62 showed a red-shift of 9 nm. The emission intensity of agZIF-62 is also significantly stronger than that of ZIF-62; thus, rapid semiquantitative detection of the content of the MOF glass in glass and crystal mixtures can be achieved. In addition, HC-agZIF-62 and MQ-agZIF-62 can transform into ZIF-62 crystals via a solvent-media mechanism. This study provides new insights into ZIF-62 glass.

Iodine Adsorption-Desorption-Induced Structural Transformation and Improved Ag+ Turn-On Luminescent Sensing Performance of a Nonporous Eu(III) Metal-Organic Framework.

Posttreatment of pristine metal-organic frameworks (MOFs) with suitable vapor may be an effective way to regulate their structures and properties but has been less explored. Herein, we report an interesting example in which a crystalline nonporous Eu(III)-MOF was transferred to a porous amorphous MOF (aMOF) via iodine vapor adsorption-desorption posttreatment, and the resulting aMOF showed improved turn-on sensing properties with respect to Ag+ ions. The crystalline Eu-MOF, namely, Eu-IPDA, was assembled from Eu(III) and 4,4'-{4-[4-(1H-imidazol-1-yl)phenyl]pyridine-2,6-diyl}dibenzoic acid (H2IPDA) and exhibited a two-dimensional (2D) coordination network based on one-dimensional secondary building blocks. The close packing of the 2D networks gives rise to a three-dimensional supramolecular framework without any significant pores. Interestingly, the nonporous Eu-IPDA could absorb iodine molecules when Eu-IPDA crystals were placed in iodine vapor at 85 °C, and the adsorption capacity was 1.90 g/g, which is comparable to those of many MOFs with large BET surfaces. The adsorption of iodine is attributed to the strong interactions among the iodine molecule, the carboxy group, and the N-containing group and leads to the amorphization of the framework. After immersion of the iodine-loaded Eu-IPDA in EtOH, approximately 89.7% of the iodine was removed, resulting in a porous amorphous MOF, denoted as a-Eu-IPDA. In addition, the remaining iodine in the a-Eu-IPDA framework causes strong luminescent quenching in the fluorescence emission region of the Eu(III) center when compared with that in Eu-IPDA. The luminescence intensity of a-Eu-IPDA in water suspensions was significantly enhanced when Ag+ ions were added, with a detection limit of 4.76 × 10-6 M, which is 1000 times that of pristine Eu-IPDA. It also showed strong anti-interference ability over many common competitive metal ions and has the potential to sense Ag+ in natural water bodies and traditional Chinese medicine preparations. A mechanistic study showed that the interactions between Ag+ and the absorbed iodine, the carboxylate group, and the N atoms all contribute to the sensing performance of a-Eu-IPDA.

Self-Standing Chiral Covalent Organic Framework Thin Films with Full-Color Tunable Guest-Induced Circularly Polarized Luminescence.

Exploring self-standing chiral covalent organic framework (COF) thin films with controllable circularly polarized luminescence (CPL) is of paramount significance but remains a challenging task. Herein, we demonstrate the first example of self-standing chiral COF films employing a polymerization-dispersion-filtration strategy. Pristine, low-quality chiral COF films were produced by interfacial polymerization and then re-dispersed into COF colloidal solutions. Via vacuum assisted assembly, these COF colloids were densely stacked and assembled into self-standing, pure chiral COF films (L-/D-CCOF-F) that were transparent, smooth, crack-free and highly crystalline. These films were tunable in thicknesses, areas, and roughness, along with strong diffuse reflectance circular dichroism (DRCD) and cyan CPL signals, showing an intrinsic luminescence asymmetric factor (glum) of ~4.3×10-3. Furthermore, these COF films served as host adsorbents to load various achiral organic dye guests through adsorption. The effective chiral transfer and energy transfer between CCOF-F and achiral fluorescent dyes endowed the dyes with strong chirality and tunable DRCD, resulting in intense, full-color-tunable solid-state CPL. Notably, the ordered arrangement of dye guest molecules within the preferentially oriented chiral pores of CCOF-F contributed to an amplified |glum| factor of up to 7.2×10-2, which is state-of-the-art for COF-based CPL materials. This work provides new insights into the design and fabrication of self-standing chiral COF films, demonstrating their great potential for chiroptical applications.

Self-Assembly of Helical Nanofibrous Chiral Covalent Organic Frameworks.

Despite significant progress on the design and synthesis of covalent organic frameworks (COFs), precise control over microstructures of such materials remains challenging. Herein, two chiral COFs with well-defined one-handed double-helical nanofibrous morphologies were constructed via an unprecedented template-free method, capitalizing on the diastereoselective formation of aminal linkages. Detailed time-dependent experiments reveal the spontaneous transformation of initial rod-like aggregates into the double-helical microstructures. We have further demonstrated that the helical chirality and circular dichroism signal can be facilely inversed by simply adjusting the amount of acetic acid during synthesis. Moreover, by transferring chirality to achiral fluorescent molecular adsorbents, the helical COF nanostructures can effectively induce circularly polarized luminescence with the highest luminescent asymmetric factor (glum ) up to ≈0.01.

Regulating the Porosity and Iodine Adsorption Properties of Metal-Organic Framework Glass via an Ammonia-Immersion Approach.

Metal-organic framework (MOF) glass is a new type of glass material, but it usually lacks sufficient porosity. Thus, regulating the pore structure of MOF glass to improve its adsorption performance is very important. Herein, we found that the porosity of MOF glasses agZIF-62 and agZIF-76 can be regulated via an ammonia-immersion approach. After ammonia immersion, the resulting agZIF-62-NH3 and agZIF-76-NH3 could be maintained in their glass states or converted to their amorphous states, respectively. Their porosity changed according to the gas adsorption experiments. Notably, compared with agZIF-62 and agZIF-76, the iodine uptake capacities for agZIF-62-NH3 and agZIF-76NH3 increased by 12 and 21 times, respectively. This work shows that the subsequent treatment of MOF glass can regulate their adsorption performance.

Assembly of a miRNA-modified QCM sensor for miRNA recognition through response patterns.

In this paper, a miRNA-based quartz crystal microbalance (QCM) biosensor was fabricated and used to the rapid and effective sensing of miRNA. The specific hybridization between probe miRNA and different selected miRNAs (miR-27a, miR-27b, and Let-7a) cause a different interaction mode, thus display different frequency change and response patterns in the QCM sensor, which were used to detect miR-27a and miR-27b. The selective sensing of miR-27a in mixed miRNA solution was also achieved. This miRNA-based QCM biosensor has the advantages of real-time, label-free, and short cycle detection.

Homochiral Cu(I) Coordination Polymers Based on a Double-Stranded Helical Building Block from Achiral Ligands: Symmetry-Breaking Crystallization, Photophysical and Photocatalytic Properties.

A pair of homochiral coordination polymers, [Cu(DPT)]n (1M and 1P, HDPT = 3,5-di-4-pyridinyl-2H-tetrazole), were assembled from achiral precursors. Crystal structure analysis showed that they are chiral three-dimensional (3D) coordination polymers based on a new double-stranded helical building block that is composed of two different 1D helices. Interestingly, rare symmetry-breaking crystallization was observed, in which the possibility of obtaining enantio-enriched bulk product with excessive M enantiomers (1-A) was obviously higher than that for P enantiomers (1-B) as demonstrated in multiple, repeated experiments with single-crystal diffraction and vibrational circular dichroism (VCD) spectra. Moreover, compound [Cu(DPT)]n shows good chemical stability in water, with pH values ranging from 3 to 13, as well as in many common organic solvents. Photophysical properties, including thermochromic properties and two-photon excited luminescence, were studied, and the potential for applications in temperature sensing was exhibited. In addition, the photocatalytic degradation of methylene blue in water indicated that compound [Cu(DPT)]n can be used as a photocatalyst.

Hydrolytically Stable Nanotubular Cationic Metal-Organic Framework for Rapid and Efficient Removal of Toxic Oxo-Anions and Dyes from Water.

Cationic framework materials capable of removing anionic pollutants from wastewater are highly desirable but relatively rarely reported. Herein, a cationic MOF (SCNU-Z1-Cl) possessing tubular channels with diameter of 1.5 nm based on Ni(II) and a nitrogen-containing ligand has been synthesized and applied to capture hazardous anionic contaminants from water. The SCNU-Z1-Cl exhibits high BET surface area of 1636 m2/g, and shows high hydrolytically stability in pH range from 4 to 10. Owing to the large tubular channels and the uncoordinated anions in the framework, the aqueous-phase anion-exchange applications of SCNU-Z1-Cl were explored with environmentally toxic oxo-anions including CrO42-, Cr2O72-, MnO4-, and ReO4-, and organic dyes. The adsorption of oxoanions exhibits high uptake kinetics and the adsorption capacities of CrO42-, Cr2O72-, MnO4-, and ReO4- are 126, 241, 292, and 318 mg/g, respectively, which were some of the highest values in the field of MOF/COF. In additional, the selectively is high when other concurrent anions are exist. The anionic dyes with different sizes including methyl orange, acid orange A, congo red, as well as methyl blue can be adsorbed by SCNU-Z1-Cl in few minutes to about 1 h. The adsorption capacities for them are 285, 180, 585, and 262 mg/g, respectively. In contrast, the adsorption kinetics for catinionic dyes with different sizes is obviously lower and exhibit a size-selectively adsorption that only cationic dye with suitable size (rhodamine B) can be adsorbed by SCNU-Z1-Cl. Consequently, SCNU-Z1-Cl can sepearate organic dyes in three different modes: size-dependent, charge-dependent, and kinetics-dependent selective adsorption. The excellent adsorption and separation properties of SCNU-Z1-Cl is attribute to the cationic framework, large tubular channel, as well as the high positive Zeta potential.

An Anionic Nanotubular Metal-Organic Framework for High-Capacity Dye Adsorption and Dye Degradation in Darkness.

A metal-organic framework (MOF), named SCNU-Z2, based on a new heterotopic tripodal nitrogen-containing ligand, has been constructed. Due to the replacement of one imidazole group in the reported ligand with one tetrazole group, the charge of the framework is changed from cationic to anionic but retains the same framework structure. The framework consists of tubular channels with a diameter of 1.5 nm and exhibits satisfactory stability in water with a pH range of 3-11. The anionic nature of the framework allows the effective adsorption of the cationic dyes MLB, CV, and RhB with capacities of 455.6, 847.4, and 751.8 mg/g, respectively. Among them, the adsorption capacities for SCNU-Z2 on CV and RhB rank as the highest when compared with other reported MOFs. In contrast, SCNU-Z2 exhibits an extremely low capacity for anionic dyes MO and AO, making it useful for the separation of anionic and cationic dyes based on a charge-dependent mode. Interestingly, SCNU-Z2 can be used to degrade an anionic dye, MB, within 30 min under darkness at room temperature. The apparent activation energy of the dye degradation reaction is calculated to be approximately 18.96 kJ·mol-1, implying that the catalytic reaction of MB can be considered as a low-temperature thermocatalytic reaction in the dark/SCNU-Z2 system.

Dimension Increase via Hierarchical Hydrogen Bonding from Simple Pincer-like Mononuclear complexes.

A tetradentate symmetric ligand bearing both coordination and hydrogen bonding sites, N(1),N(3)-bis(1-(1H-benzimidazol-2-yl)-ethylidene)propane-1,3-diamine (H2bbepd) was utilized to synthesize a series of transition metal complexes, namely [Co(H2bbepd)(H(2)O)2]·2ClO(4) (1), [Cu(H2bbepd)(OTs(-))]·OTs(-) (2),[Cu(bbepd)(CH(3)OH)] (3), [Cd(H(2)bbepd)(NO3)2]·CH(3)OH (4), [Cd(H(2)bbepd)(CH(3)OH)Cl]·Cl (5), and [Cd(bbepd)(CH(3)OH)2] (6). These complexes show similar discrete pincer-like coordination units, possessing different arrangements of hydrogen bonding donor and acceptor sites. With or without the aid of uncoordinated anions and solvent molecules, such mononuclear units have been effectively involved in the construction of hierarchical hydrogen bonding assemblies (successively via level I and level II), leading to discrete binuclear ring (complex 2), one-dimensional chain or ribbon (complexes 3, 4 and 6) and two-dimensional layer (complexes 1 and 5) aggregates.

Synthesis and enantioseparation behaviors of novel immobilized 3,5-dimethylphenylcarbamoylated polysaccharide chiral stationary phases.

Two new polysaccharide-derived chiral selectors, namely, 6-azido-6-deoxy-3,5-dimethylphenylcarbamoylated amylose and 6-azido-6-deoxy-3,5-dimethylphenyl carbamoylated cellulose, were synthesized under homogeneous conditions and immobilized onto aminized silica gel by the Staudinger reaction, resulting in two new immobilized polysaccharide chiral stationary phases (CSPs). Their enantioseparation performances were investigated under normal-phase mode by HPLC. Among 17 analytes, baseline separations of 12 pairs of enantiomers are achieved on the immobilized cellulose CSP, which demonstrates that this new cellulose material exhibits almost the same enantioseparation performance as the coated cellulose CSP. In addition, the amylose-derived CSP presents limited enantiorecognition ability but certain complementarity with the immobilized and coated cellulose-based materials. Neither metolachlor nor paclitaxel side chain acids are separated on two cellulose-derived CSPs, but effective separations are obtained on the immobilized amylose column.

Construction of binary metal-organic cage-based materials via a "covalently linked plus cage encapsulated" strategy.

A strategy for constructing binary metal-organic cage (MOC)-based materials was developed. The cationic MOCs were covalently linked by organic linkers to a cationic extended network, whereas the anionic MOCs acted as counterions and were encapsulated in the network. Compared with the corresponding unary materials, the binary MOC-based materials exhibited improved porosity and adsorption performance.

Construction of a Defective Chiral Covalent Organic Framework for Fluorescence Recognition of Amino Acids.

The design and synthesis of chiral covalent organic frameworks (COFs) with controlled defect sites are highly desirable but still remain largely unexplored. Herein, we report the synthesis of a defective chiral HD-TAPB-DMTP COF by modifying the chiral monomer helicid (HD) into the framework of an achiral imine-linked TAPB-DMTP COF using a chiral monomer exchange strategy. Upon the introduction of the chiral HD unit, the obtained defective chiral HD-TAPB-DMTP COF not only displays excellent crystallinity, large specific surface area (up to 2338 m2/g) and rich accessible chiral functional sites but also exhibits fluorescence emission, rendering it a good candidate for discrimination of amino acids. Notably, the resultant defective chiral HD-TAPB-DMTP COF can be used as a fluorescent sensor for enantioselective recognition of both tyrosine and phenylalanine enantiomers in water, showing enhanced fluorescent responses for the L conformations over those of the D conformations with the enantioselectivity factors being 1.84 and 2.02, respectively. Moreover, molecular docking simulations uncover that stronger binding affinities between chiral HD-TAPB-DMTP COF and L-tyrosine/L-phenylalanine in comparison to those with D-tyrosine/D-phenylalanine play important roles in enantioselective determination. This work provides new insights into the design and construction of highly porous defective chiral COFs for enantioselective fluorescence recognition of amino acids.

Metal-organic framework derived heterostructured phosphide bifunctional electrocatalyst for efficient overall water splitting.

Developing high active and stable cost-effective bifunctional electrocatalysts for overall water splitting to produce hydrogen is of vital significance in clean and sustainable energy development. This work has prepared a novel porous unreported MOF (Ni-DPT) as a precursor to successfully synthesize a non-noble bifunctional NiCoP/Ni12P5@NF electrocatalyst through doping strategy and interface engineering. This catalyst is constructed by layered self-supporting arrays with heterojunction interface and rich nitrogen-phosphorus doping. Structural characterizations and the density function theory (DFT) calculations confirm that the interface effect of NiCoP/Ni12P5 heterojunction can regulate the electronic structure of the catalyst to optimize the Gibbs free energy of hydrogen (ΔGH*); simultaneously, the defect-rich layered nanoarrays can expose more active sites, shorten mass transfer distance, and generate a self-supporting structure for in-situ reinforcing the structural stability. As a result, this NiCoP/Ni12P5@NF catalyst exhibits favorable electrocatalytic performance, which simply needs overpotentials of 100 mV for HER and 310 mV for OER, respectively, at a current density of 10 mA·cm-2. The anion exchange membrane electrolyzer assembled with this NiCoP/Ni12P5@NF as both anode and cathode catalysts can operate stably for 200 h at a current density of 100 mA·cm-2 with an insignificant voltage decrease. This work may provide some inspiration for the further rational design of inexpensive non-noble multifunctional electrocatalysts and electrode materials for water splitting to generate hydrogen.

Primary Amine-Functionalized Chiral Covalent Organic Framework Enables High-Efficiency Asymmetric Catalysis in Water.

Aqueous asymmetric catalysis using chiral covalent organic frameworks (COFs) represents a significant advancement but remains to be explored. Herein, we present the first example of aqueous asymmetric catalysis catalyzed by a primary amine-tagged chiral D-ADP-TAPB COF. The D-ADP-TAPB COF was synthesized by the postsynthetic deprotection of D-ADP-TAPB-Boc bearing a protective tert-butoxycarbonyl (Boc) group, which was constructed by a Schiff-base reaction between an alanine-derived chiral building block (D-ADP-Boc) and 1,3,5-tris(4-aminophenyl)benzene (TAPB). The crystalline D-ADP-TAPB COF exhibits a uniform, spherical morphology with abundant, well-distributed chiral primary amines, rendering it highly active in the asymmetric aldol reaction between cyclohexanone and 4-nitrobenzaldehyde. Notably, this reaction is conducted entirely in water, achieving impressive yields and enantiomeric excess (ee) values of up to 90 and 85%, respectively. To the best of our knowledge, D-ADP-TAPB COF represents the first chiral COF catalyst with high reactivity and enantioselectivity for an asymmetric aldol reaction solely in water, eliminating the need for conventional organic solvents. Moreover, a plausible mechanism for D-ADP-TAPB COF-mediated aqueous asymmetric aldol reactions is elucidated. This work not only expands the toolbox for designing rare primary amine-functionalized chiral COFs for asymmetric catalysis but also opens exciting avenues for developing green and water-based enantioselective catalysis.

Hierarchical porous amorphous metal-organic frameworks constructed from ZnO/MOF glass composites.

For the first time, hierarchical porous amorphous metal-organic frameworks (HP-aMOFs) containing ultramicropores, micropores, and mesopores were synthesized by etching a composite of MOF glass (agZIF-76) and ZnO using ammonia. These materials show potential applications in the adsorption of C2 hydrocarbons.

Raising the Asymmetric Catalytic Efficiency of Chiral Covalent Organic Frameworks by Tuning the Pore Environment.

Chiral covalent organic frameworks (COFs) hold considerable promise in the realm of heterogeneous asymmetric catalysis. However, fine-tuning the pore environment to enhance both the activity and stereoselectivity of chiral COFs in such applications remains a formidable challenge. In this study, we have successfully designed and synthesized a series of clover-shaped, hydrazone-linked chiral COFs, each with a varying number of accessible chiral pyrrolidine catalytic sites. Remarkably, the catalytic efficiencies of these COFs in the asymmetric aldol reaction between cyclohexanone and 4-nitrobenzaldehyde correlate well with the number of accessible pyrrolidine sites within the frameworks. The COF featuring nearly one pyrrolidine moiety at each nodal point demonstrated excellent reaction yields and enantiomeric excess (ee) values, reaching up to 97 and 83%, respectively. The findings not only underscore the profound impact of a deliberately controlled chiral pore environment on the catalytic efficiencies of COFs but also offer a new perspective for the design and synthesis of advanced chiral COFs for efficient asymmetric catalysis.

Effect of chromatographic conditions on enantioseparation of bovine serum albumin chiral stationary phase in HPLC and thermodynamic studies.

Twelve chiral compounds were enantiomerically resolved on bovine serum albumin chiral stationary phase (BSA-CSP) by high-performance liquid chromatography (HPLC) in reversed-phase modes. Chromatographic conditions such as mobile phase pH, the percentage of organic modifier, and concentration of analyte were optimized for separation of enantiomers. For N-(2, 4-dinitrophenyl)-serine (DNP-ser), the retention factors (k) greatly increase from 0.81 to 6.23 as the pH decreasing from 7.21 to 5.14, and the resolution factor (R(s)) exhibited a similar increasing trend (from 0 to 1.34). More interestingly, the retention factors for N-(2, 4-dinitrophenyl)-proline (DNP-pro) decrease along with increasing 1-propanol in mobile phase (3%, 5%, 7% and 9% by volume), whereas the resolution factor shows an upward trend (from 0.96 to 2.04). Moreover, chiral recognition mechanisms for chiral analytes were further investigated through thermodynamic methods.

Reversal of elution order of N-(2,4-dinitrophenyl)-proline and N-(2,4-dinitrophenyl)-serine in HPLC by BSA chiral stationary phase.

N-(2,4-dinitrophenyl)-proline and N-(2,4-dinitrophenyl)-serine were enantiomerically resolved on the BSA chiral stationary phase by HPLC in reversed-phase mode. Effects of chromatographic conditions on enantioseparation and elution order have been investigated in detail. For these two samples, reversal of enantiomer elution order was observed by changing buffer pH, the content of acetonitrile, or alcohol modifiers in mobile phase, which is firstly reported in the BSA chiral stationary phase studies. More interestingly, combined effect between buffer pH and the content of acetonitrile was also observed. In addition, coelution range of enantiomers varied along with the content of acetonitrile in mobile phase.